A study on the effect of secondary electron emission, which strongly affects the detection of extreme-UV radiation, was performed on diamond detectors. Two different structures were compared: interdigitated contacts and a transverse Schottky diode configuration. Both devices were electrically characterized by I-V measurements and their responsivity was measured in the extreme UV spectral region (20–120 nm) by using He-Ne gas discharge radiation sources and a toroidal grating vacuum monochromator. Through an ad-hoc measurement configuration, the contributions of the internal photocurrent and of the photoemission current have been analyzed and separately evaluated. The results showed that secondary electron emission, which clearly depends on the experimental conditions (e.g., external electric field, pressure, etc.), is one of the most relevant processes affecting the spectral responsivity in the extreme UV band. In particular, for interdigitated devices, extreme care must be taken in order to obtain an absolute value of their responsivity, while detectors in the transverse configuration can be shielded in such a way to avoid secondary electron current contribution and therefore provide a more correct and reliable response.